Acrylic esters of halogenated acetylenic diols

ABSTRACT

The esters disclosed herein comprise polymerizable acrylic esters of the halogenated acetylenic alcohols, WHEREIN R represents hydrogen preferably or a monovalent hydrocarbon containing one to 10 carbon atoms, X is a halogen selected from the class consisting of chlorine and bromine, y represents an integer having a value of 1 or 2, and one n represents zero and the other n represents an integer having a value of 0 to 3, preferably zero. These acrylic monomers are useful for the preparation of self-extinguishing homopolymers and copolymers; the diesters are also particularly useful as crosslinking agents for other monomers and polymers.

United States Patent DAlelio [54] ACRYLIC ESTERS OF HALOGENATEDACETYLENIC DIOLS [72] Inventor: Gaetano F. DAlelio, 2011 East Cedar St.,

South Bend, 1nd. 46617 [22] Filed: Dec. 19, 1968 [21] App1.No.: 785,337

[52] US. Cl ..260/89.5, 117/145, 117/148,

[56] References Cited UNITED STATES PATENTS Verbanic et a1 ..260/486 HGobran et a1. ...260/486 H Groves ..260/89.5 H

Primary Examiner-Harry Wong, Jr. Attorney-Walter J. Monacelli 1451 May23, 1972 ABSTRACT The esters disclosed herein comprise polymerizableacrylic esters of the halogenated acetylenic alcohols,

CR OCHRCHR OH I 1 wherein R represents hydrogen preferably or amonovalent hydrocarbon containing one to ten carbon atoms, X is ahalogen selected from the class consisting of chlorine and bromine, yrepresents an integer having a value of l or 2, and one 11 representszero and the other n represents an integer having a value of 0 to 3,preferably zero. These acrylic monomers are useful for the preparationof self-extinquishing homopolymers and copolymers; the diesters are alsoparticularly useful as cross-linking agents for other monomers andpolymers.

14 Claims, No Drawings 1 2 ACRYLIC ESTERS F HALOGENATED ACETYLENICreaction with aldehydes and ketones, such as for example, DIOLS withCHgO, CH CHO, CJ-I CHO, C H CHO, C,H ,CHO, C H CHO, C H CHO, C H CHO, CHCH CHCHO, PRIOR ART cn-ncn CHCHO, cmcocr-n, c,1-i,cocH,, cn coc n Norelated prior art is known. Copending application =1 1 21 lo 2h asfollows: (DA-551) Ser. No. 785,336 filed the same date herewith dis- R Rcloses related acrylic esters of halogenated acetylenic monoal- H0 0}:2R 0 0 H0 J3CEC- -0H cohols. l l

A v R R (D) BACKGR UND F THE I TI en, in formula (C both ns are zero andy is 2, these This invention deals with polymerizable acrylic esterswhich acetyleslc dlols havc the formula H0CR'CH3C contain halogen atomsin their structures. In general, it conzcRzO 3 are prepared by reactingacetylene Oxlrane cems monoand diacrylic esters of polyhalogenatedcompoun acetylenic diols. In particular, it deals with the acrylic-type5 K R esters of halogenated ethylenic diols selected from the class of 0HOCHRCHRO CR CX=OX OR OCHRCHR OH 1 77 1. and (A) HOCHRCHRO CRCX OX CROCHRCHR-OH /T( A. .h a HJP'L In the above formulas, R representshydrogen preferably or such as a monovalent hydrocarbon containing oneto 10 carbon atoms, X is chlorine or bromine, y has a numerical value ofl or 2, and one n represents zero and the other n is an integer O O 0having a value of 0 to 3. When the other n is also zero, the CUHIOCHOH?CNHHCHCHQ CNHZICHCHCHK CGHHCHCHZ' ester symmetrical and IS preferablefor the practice of this invention. Copending application Ser. No.785,338 (Docket 3o 0 O O DA-552B) filed the same date herewith, coversother symetc-1 as metrical compounds in which n is l, 2 or 3. H0 5 OH 2R2 Typical esters of the invention are those in which one or both of thealcoholic hydroxyl groups in formulas (A) and (B) H0R2C R CHECHCRZC RzQH(E) have been replaced y an y y group of the formula, 3 5 The reactionof the acetylenic alcohols of formulas (D) and (E) with OH COO- OHROHR vi 4 V" i i H O wherein R represents hydrogen, methyl and the halogen X40 as defined hereinabove. These esters are readily prepared by tyleldthc acetylenic dialcohols thus! csterifying the alcohols of formulas (A)and (B) with the Formuhw) HCHRCHR mw acrylic chlorides, anhydrides oracids, Cl-l C(R)COC1, [Cl-l C(R)CO] O and CH C(R)COOH, respectively, byprocedures well known in the art. When the acid Formula (E) nCHRCI-IRFormula (C) chloride is used, a hydrohalide acceptor, such as a tertiaryamine, as for example, the trialkylamines, dimethylaniline and thelikeisf bl usedin the reaction. The acrylic esters of this invention can beformulated as The halogenated dialcohols of formulas (A) and (B) fromhaving the Structures which the acrylic esters of this invention areprepared are obrained very readily by the reaction of bromine orchlorine with the acetylenic alcohols corresponding to these formulas. j/y When 1 mole of halogen is reacted with the acetylenic dialcohol, thedihalo-compound is obtained, whereas when 2 CX=CX(CR -(0CHRCHR P molesof halogen are reacted, the tetrahalo compound is obj tained: V g

X HO CHRCHRO (CRz CEC(CRz (OCHRCHR OH /n /y j) j X HO -CHRCHRO (0R2oX=cX- CRz (0CHROHR 0H A A A 1.

(A) (CR CXzCX (CR (OGHRCI-IR OH A 1y 1y 1.1 a f The alcohols of Formula(C) are derivatives of acetylene, 2= -TCHRCHRO (CRz easily prepared fromacetylene, and a number of which are commercial products. When inFormula (C) both n's are zero (J and y is one, these acetylenic diolshave Formula (D), (I 2 X2 I HOCR C CCR OH, and are prepared fromacetylene by (G) wherein P represents OH and CH C(R')COO- and in whichR, R, n, y and X have the same meaning as defined hereinabove.

Typical R hydrocarbon groups are methyl, ethyl, propyl, butyl, amyl,hexyl, heptyl, nonyl, decyl, phenyl, tolyl, xylyl, ethylphenyl,naphthyl, methylnaphthyl, phenethyl, benzyl, phenylpropyl,naphthylmethyl, cyclohexyl, cycloheptyl, methylcyclohexyl,ethylcycloheptyl, cyclohexylethyl, etc.

The esters of this invention are useful with their halogen content asflame retardants and for the preparation of flameretardant compositions.They are particularly useful for the preparation of homopolymers as wellas copolymers with other vinyl type monomers, including other esters ofthis invention. Also, these esters find utility not only as monomers butalso as plasticizers and fire-retardant additives to other non-polymericas well as polymeric materials. Especially are they suited as the vinylmonomer, alone or with other monomers, for coreaction with theunsaturated polyesters, typical examples of which are the polyalkylenemaleates and fumarates, as well as those unsaturated polyesters modifiedby non-olefinic polycarboxylic acids such as phthalic,tetrachlorophthalic, tetrabrornophthalic or chlorendic anhydride.

The polymerizable monomers of this invention, as illustrated, forexample, by the acrylate, methacrylates, etc., are readily polymerizedor copolymerized to polymers by radical generating initiators, such asthe peroxides, hydroperoxides, peracetates or by redox systems includinghydrogen peroxide with ferrous salts or sodium bisulfite, potassium orsodium persulfate with bisulfate, etc.; ultraviolet light, etc. Radicalpolymerizations are well known in polymer science and are applicable tothe monomers of this invention.

The product of soluble polymers, especially from the monoacrylic estersof formula (F),

CH2C(R )COO \CHRCHIKf/n CRTCX OX CR)L which contain two double bonds issurprising, particularly since other acrylic esters having two doublebonds, such as CH CHCOOCH CH CH and CH CHCOOCH C CH, crosslink underradical polymerization as shown in J. Polymer Sci., 5, 323-337, 813-832,994,ll4 (1967).

The solubility of polymers of Formula (H) permits them to be used asmodifiers of other polymers, for example, as a coreactant inpolyurethane formulations.

Furthermore, the new esters of this invention cannot be prepared byfirst synthesizing the acrylic esters of the acetylenic diols and thenhalogenating the acrylic ester, because the halogenation is notselective and causes halogenation, simultaneously, of all or most of thevinyl bonds in the acrylic ester, thereby destroying thepolymerizability of the compound, for example,

The monomers of this invention homopolymerize and copolymerize readilysuch as by means of radical type initiators, ultraviolet light, ionizingradiation or thermally. The homopolymerizations and copolymerizationsmay be performed (1) in mass, that is, neat, in the absence of addedsolvents or dispersion media; (2) in suitable organic substances whichare solvents for the monomers as well as the polymers, or which aresolvents for the monomers and not for the polymers, in which cases thepolymers precipitate from the media; or (3) in emulsion systems whichare well known in the art and which comprise an emulsifying agent suchas soaps, synthetic emulsifiers, such as dodecylbenzene sulfonatesodiurn salts, sodium sulfodioctylsuccinate and the like, in water. Inthe emulsion systems, water-soluble radical initiators such as potassiumpersulfate, hydrogen peroxide, sodium perborate, urea peroxide, etc.,are used alone or in the presence of a redox agent, such as sulfurdioxide, sodium bisulfite, fer- (O CHRCHRg-OH rous sulfate, etc.

Thus, the polymers and copolymers of this invention can be prepared bythe vinyl type polymerization by means of radical initiators such as theperoxy and azo catalysts as such or as redox systems as well as byultraviolet and ionizing radiation. Of the azo-type catalysts,azobisisobutyronitrile is a typical example and is especially preferred.The peroxy catalysts are illustrated by stearoyl, lauroyl and butyroylperoxide but for economic reasons benzoyl peroxide, tertiary butylperoxide and tertiary butyl peracetate are preferred, but any of theother well-known peroxy catalysts such as cumene peroxide and the likecan also be used.

The diacrylic esters yield insoluble crosslinked polymers andcopolymers, whereas the monoacrylic esters yield soluble polymers.

When solutions of the non-crosslinked polymers are desired, they can beobtained readily by polymerization in a suitable organic solvent or amixture of organic solvents such as methyl acetate, ethyl acetate,acetone, methylethyl ketone, methylisobutyl ketone, benzene, toluene,xylene, dioxane, tetrahydrofuran, chloroform, carbon tetrachloride,ethylenedichloride, dibutyl ether, etc. In such cases a solution of 5 to75 percent of the monomer in the solvent is used.

When low molecular weight polymers are desired, the amount of radicalinitiator used may be as high as 3 to 4 percent by weight of the monomeror comonomers used; and the molecular weight may be further controlledby the use of radical chain transfer agents such as chloroform, carbontetrachloride, octyl mercaptan, dodecyl mercaptan and the like.

When high molecular weight polymerization products are desired, thepolymerizations are performed preferably in the absence of chaintransfer agents and only sufficient initiator to overcome the inductionperiod of the system, such as of the order of 0.025 to 0.1 percent byweight of initiator. Alternately, the polymerization may be achievedthermally, simply by heating to generate the initiating radicals.

The polymerization can be performed over a wide range of temperaturesdepending upon whether the system is a mass, a solution or an emulsionpolymerization and whether the initiation is by a redox system,ultraviolet or ionizing radiation. With ionizing radiation,polymerization can be achieved at -40 C, the redox polymerizations canbe performed at 0 to C.; and the thermal polymerizations can beperformed up to temperatures of the order of lO0-125 C. or higher.

The new monomers of this invention can be copolymerized with other vinylmonomers, such as the acrylic and methacrylic esters such as the methyl,ethyl, propyl, butyl, hexyl,

cyclohexyl, dodecyl, etc. esters. In addition to, or in lieu of theseacrylic-type esters used in copolymerization to prepare the startingpolymer, any other copolymerizable monovinyl or monovinylidene comonomeror mixtures thereof can be used, for example, the vinyl esters, that is,vinyl acetate, and the monovinyl esters of saturated and unsaturated,aliphatic, monobasic and polybasic acids, and more specifically thevinyl esters of the following acids: propionic, isobutyric, valeric,caprylic, caproic, oleic, stearic, acrylic, methacrylic, crotonic,oxalic, malonic, succinic, glutaric, adipic, suberic, azelaic, maleic,fumaric, itaconic, mesaconic, hexahydrobenzoic, citric, trimesic, etc.,as well as the corresponding allyl, methallyl, etc. esters of theaforementioned acids, methacrylic acid, hydroxy propyl methacrylate,etc.; itaconic acid monoesters and diesters, such as the methyl ethyl,butyl esters, the maleic and fumaric acid monoesters, diesters and theiramide and nitrile compounds, such as diethyl maleate, maleyl diamide,

fumaryl dinitrile, dimethyl fumarate, etc.; acrylonitrile,methacrylonitrile, etc.; ethers such as methallyl ethyl ether, vinylethyl ether, vinyl butyl ether, allyl propyl ether; cyanuric acidderivatives having one copolymerizable unsaturated group attacheddirectly or indirectly to the triazine ring, such as allyl diethylcyanurate, vinyl diethyl cyanurate, as well as the partial, soluble orfusible polymerizable polymers of the hereinabove listed monomers, etc.

Typical suitable aromatic comonomers include vinyl aryl compounds suchas styrene, vinyl naphthalene, vinyl toluene, vinyl xylene, vinylphenol, vinyl ethyl benzene, vinyl dimethyl naphthalene, vinyl diphenyl,etc., vinyl phenyl ether, vinyl benzoate, vinyl naphthoate, vinyl methylphthalate, allyl ethyl phthalate, allyl propyl phthalate, etc.

The polymeric compositions of this invention are particularly useful incoating compositions on all types of substrates, including cellulose inits various forms, such as paper, wood, paper board, wood board, woodpulp, regenerated cellulose in film or fiber form, laminates of varioustypes including those prepared from fibrous fillers bonded with urea,melamine, epoxy and polyester resins, plaster board, concrete in itsvarious forms such as slabs, blocks and the like. They may also be usedas impregnants for porous bodies such as the compositions hereinabovenamed, as well as for synthetic and natural sponges, etc. Particularlydo they find use as bonding agents and adhesives for solid, porous andfoamed bodies. They can be used alone or admixed with each other or withother copolymerizable monomers, unsaturated or saturated polymers, inthe absence or presence of dyes, pigments, plasticizers. For coating,impregnating or adhesive compositions where the presence of smallamounts of solvent in the cured composition is not objectionable theycan be mixed with volatile or non-volatile solvents best suited to theparticular application.

The polymers of this invention are also useful in the preparation ofcopolymers with unsaturated alkyd resins. In carrying this portion ofthe invention into effect, an esterification product of a polyhydricalcohol and an C1,!1-UI1S8IUI3I6d polycarboxylic acid is first preparedin accordance with techniques now well-known to those skilled in thealkyd resin art, such as ethylene glycol maleate, propylene glycolmaleate, ethylene glycol maleate-phthalate, ethylene glycolmaleateacrylate, propylene glycol-fumarate-methacrylate and the like.

In many cases, instead of copolymerizing a single monomer of thisinvention with a single alkyd resin, mixtures can be used of two or moresuch monomers with a single alkyd resin, or a single monomer can be usedwith two or more alkyd resins or a mixture of two or more monomers withtwo or more alkyd resins.

The polymers of this invention can be used alone or with fillers, dyes,pigments, opacifiers, lubricants, plasticizers, natural and syntheticresins or other modifying bodies in, for example, casting, molding,laminating, coating applications, and as adhesives, impregnants andprotective coatings.

in preparing copolymers, the monomers of this invention can constituteas much as 98995 percent by weight of the whole, or the modifyingcomonomer or alkyd resin can constitute 98-995 percent of the whole.

In general, the proportions of the components used in a particularformation will depend upon the particular properties desired in theinterpolymer. For most applications, it is preferred to use to 80percent of the monomers of this invention and from 80 to 20 percent ofthe modifying polymer or monomer, since within these rangesinterpolymers best adapted for most commercial applications can beproduced.

Within these ranges the new interpolymers have a wide range ofproperties. For example, depending upon the particular crosslinkingpolymer and any modifying polymer or monomer, the particular proportionsthereof, the conditions of polymerization, such as the temperature,pressure, presence or absence of additives, etc., and the extent ofpolymerization, they can vary from soft flexible bodies to hard rigidmasses of varying resistance to solvents.

For coating or impregnating applications where the presence of a smallamount of solvent in the cured composition is not objectionable, themixed starting component can be diluted with volatile or nonvolatilesolvents or diluents best suited for the particular service application,and then can be polymerized after the application of the solution to theparticular article to be coated or impregnated, or impregnated andcoated. By suitable selection of the starting material and theconditions of the interpolymerization, interpolymers can be obtained inan insoluble, infusible state practically resistant to the destructiveeffect of other chemical bodies, such as acid, bases, salts, solvents,swelling agents, and the like.

When it is desired to modify the properties of the crosslinkablemonomers of this invention, this can be accomplished by copolymerizing amixture comprising at least one such polymer with at least onecopolymerizable monomer containing at least one unsaturated ethylenic,or acetylenic hydrocarbon radical, more particularly, a

CHz=C radical, such as vinyl, allyl, methallyl, vinylidene, etc., orwith a copolymerizable compound containing a -CH CH-, or a grouping, forexample, as in vinylidene fluoride, vinylidene cyanide, vinylpropionate, maleic anhydride, or its esters and amides, methyl maleicanhydride, tetrafluoroethylene, etc.

Additional examples of copolymerizable comonomers are monomeric orpartially polymerized vinyl esters, such as the acetate, propionate,etc., vinyl ketones, methyl vinyl ketones, olefinic nitriles, such asacrylonitrile, methacrylonitrile, fumaryl nitrile,beta-cyano-ethylacrylate, acrylic and methacrylic esters, for example,methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, ethylmethacrylate, propyl methacrylate, butyl methacrylate, octylmethacrylate, glycol dimethacrylate, allyl methacrylate, etc.; itaconicesters, for example, diamyl itaconate, divinyl itaconate, diallylitaconate; olefinic amides, for example, acrylamide, itaconamide, themaleic monoand diamides, and the corresponding imides, etc., the vinylethers, for example, vinyl hexyl ether, vinyl isobutyl ether, vinylcyclohexyl ether, the dienes, etc., for example, butadiene, isoprene,dimethyl butadiene, etc., the o-, mand p-methyl and chloro styrenes,etc.

In preparing copolymers of the crosslinkable monomers with polymerizablecomonomers such as methyl methacrylate, styrene, acrylonitrile, and thelike, the crosslinkable polymer can constitute as little as 0.1 percentby weight of the whole, whereas in other cases the crosslinkablepolymers can constitute as much as 98-99 percent of the whole. Theproportion of the components in a particular formulation will dependupon the particular comonomers used and the particular propertiesdesired in the copolymer. The polymers and copolymers can be preparedmost readily by ionizing radiation.

The acrylic monomers of this invention are particularly suitable forgrafting to polymers in fiber form, by techniques well-known in the artto render the fibers non-burning, such as to the polymer fibers andtextiles of nylon, polyvinyl alcohol, regenerated cellulose, cotton,etc. One particularly useful method is to form a redox metal complex ofeither acidic cellulose or a xanthated cellulose and to graft themonomer directly to the cellulose.

Various methods of practicing the invention are illustrated by thefollowing examples. These examples are intended to illustrate theinvention and not in any sense to limit the manner EXAMPLE I a. To 86parts of 2-butyne diol, HOH C *3 CCH OH, in 350 parts of CCL, is addedslowly with stirring at -25 C. l6] parts of bromine in 625 parts of COand the reaction allowed to continue, after the bromine addition, for 3hours at 25-40 C. The reaction mixture is then washed first with aqueous10 percent Na CO then with distilled Water following which, the CG.layer is separated, dried over anhydrous sodium sulfate, decolorizedwith activated carbon, filtered, and the CC], removed by distillation atreduced pressure, leaving an almost quantitative yield of HOCl-l cBrCBrCl-hOl-l, melting point on recrystallization, li6.51 17 C. Theelemental analysis yields values of 19.47 percent C and 65.06 percentBr, which are in good agreement with the theoretical values.

b. When procedure (a) above is repeated using 322 parts of bromineinstead of 161 parts, there is obtained the tetrabromo derivative, HOCHCBr CBr- CH OH, 78.7 percent bromine, which is in close agreement withthe theoretical value.

c. Into a stirred solution of 86 parts of HOH CC E CCH OH in 500 partsof CCl,,, maintained at 10-l5 C., is slowly passed a stream of chlorineuntil 71 parts of Cl are reacted. Then the solution is purified by theprocedure of Example 1(a) above, yielding HOCI-l CCl CCICH OH, m.p. 78C., which on analysis for chlorine yields a value of 45.26 percent,which is close to the theoretical value for the compound.

Br Br d. The above procedures are typical of those used to prepare thefollowing dihaloand tetrahalo-diols from which the acrylic esters areprepared.

Bromination of this compound by the procedure given in Example l( a)yields the product EXAM PLE ii The following is a typical procedure forpreparing diesters of the halogenated diols.

To a mixture of 800 parts of dry benzene, 1 part of tertiary butylcatechol, 1 mole of halogenated diol and 2 moles of triethylamine,cooled to 5 C., there is added slowly with stirring two moles of theacid chloride (209 parts of CH C(CHQCOC] or 181 parts of CH CHCOCl) overa period of 2 hours. The mixture is then filtered to removetriethylamine hydrochloride and hexane is added to the filtrate untilthe solution becomes turbid. The solution is again filtered, decolorizedwith activated carbon and further purified by passing the solutionthrough a column of chromatographic alumina or silica. The solvent isthen removed from the solution at reduced pressure of l to mm Hg leavingthe diester as a clear, viscous oil. The diesters so prepared can beused directly, but if further purification is desired or required, suchpurification is readily accomplished in a falling film evaporator. Theanhydrides of acrylic and methacrylic acid, [Cl-l C(R)CO] O, can be usedinstead of the acid chlorides. By the use of the above procedure, theacrylic esters and the methacrylic esters of dihalo-diols, (1) to (11)inclusive, and of the tetrahalo-diols, (a) to (h) inclusive, are readilyprepared, whose elemental analyses for halogen are in good agreementwith the calculated values, as illustrated by the analysis of sometypical diesters.

Similarly, the chloroacrylic esters and the bromoacrylic esters areprepared by using the halogenated acid chlorides, CH C(Cl)COCl and CH,C(Br)COCl, respectively.

EXAMPLE Ill To a mixture of 500 parts of dry benzene, 1 part of tertiarybutyl catechol, 59 parts of trimethylamine, and 250 parts of HOCH CBrCBrCH- OH, cooled to 5 C., there is added slowly with stirring over aperiod of 4 hours, parts of CH,

. HOC(CHa)rCBr=CBrC(CHahOH g,

Percent Number Structure halogen 1 41.85 O :=CHOOOCH=OH OB1-.J

1 38.48 [CH2=CHCOOC(CH:)2CBrj CH2=CHCOOC(CH3)gCCl:l

MAJ. 1 41. 9o

CHz=C(CH3)COOCH CBrJ [C F-cwlincoocmccl [CHi=C(OH3)OOOCH2CH2CBrJCH2=C(CHa)COOC(CHa)gCB:|

OHFC(CHZ)COOC(CHJ)2CCIJ MAJO "1 30.[CHFC(CH3)COOCH(CH3)CHg0CH(CH3)CH10CB!':-|:

A.& 62.01

CH2=CHCOOCH2CBH l [CHFCHCOOCH2CClT [CHFCHCOOC(CH3)2CBI'2TCHg=CHCOOC(CHs)2CC12J- MA.a. l 58. 58

CH2=C (CHQCOOCHZCBQT MA.b I 38.60

OHFC(CH )COOCH;CClg

MA.d t 53.00,

[CH2=C(CH3)COOC(CH3)2CBT2 I MA.f. 33.70

CHFC(CHa)COOC(CH3)2CClz-T CHCOCl. The mixture is then filtered to removeprecipitated trimethylamine hydrochloride, and hexane is added to thefiltrate until the solution becomes turbid, is then refiltered,decolorized with activated carbon and passed through a chromatographiccolumn of silica. The benzene is then removed at l to 5 mm Hg pressureleaving the product as a clear viscous oil. lts infrared spectrum showsstrong bands for a free hydroxyl in the 3 micron region along with thetypical bands expected for the acrylic ester linkages in the 12.34 1.1.region. Vapor phase chromatography indicates that the product consistsprimarily of monoester and about 11.2 percent of diester whichcorresponds to A1 of Example ll. Separation of the monoand diesters isaccomplished readily in a falling film evaporator at 0.05 mm Hgpressure. The elemental analysis of 39.43 percent bromine for thefraction showing the freehydroxyl group, is in good agreement with thecalculated value for the compound, CH CHCOOCH CBr CBrCH- OH. By theabove procedure the acrylic-type esters of the dihalo-diols, (l) to (ll) inclusive, of the tetrahalo-diols,

(a) to (h) inclusive, are readily prepared, These are converted to theethylene glycol, diethylene glycol and triethylene glycol derivatives byreacting the hydroxy group with l, 2 and 3 moles of ethylene oxide inthe presence of a small amount of sodium hydroxide. These monohydroxyderivatives are then converted by reaction of the respective terminalhydroxy groups with acrylyl chloride to diacrylates of this invention inwhich the second n of the formula is l, 2 or 3.

Various typical derivatives are illustrated as follows:

(11) CHz=CHC O O OH2Br=CBrCHzO CHzQHzOH (12) CHFOHC O O CHzCBr=CBrCH (OCHzCH2) 20H (13) CHFCHC O O CH2CBr=CBrGH2(O CH2CH2)3OH (15) CH2=CHC O OCH2CBr=CBrCH2O CH2CH2O O C CH=CH2 (16) CH2=CHC O O CHzCBr=CBrCHg(OCHrCHz) O O C CH=CH2 (l7) CH2=CHCOOCH2CBr=CBrCH2(OCH CHQMOOCCH=CH2 (18)CH =CHCOOCH2CI3r2CBr2CH2OCHaCHzOOCCH=CH2 (19)HOCHzCBr=CBrCH2OCH2CH2OOCCH=CH2 (20) IIOCHZCCICC1CH2(OCHQCHZ)QOOCCH=CH2(21) IIOCHzCBrQ CPECE QQCHzCH2Z QQQCH=CH2 EXAMPLE IV The followingunsaturated polyesters are prepared, as illustrative of the class ofunsaturated alkyd resins, by heating the ingredients in an inertnitrogen or carbon dioxide atmosphere.

Alkyd Resin A Ethylene glycol maleate (parts by weight) Ethylene glycol68.0 Maleic anhydride 98.0

The components are mixed and slowly heated in the course of 1 hour to180 C. and held at this temperature for 4 to 6 hours, until the acidnumber is reduced to below 40.

Ethylene glycol- Alkyd Resin B maleate-phthalate (parts by weight)Ethylene glycol 68.2 Maleic anhydride 49.0 Phthalic anhydride 74.0

The compounds are mixed and heated according to the procedure givenabove for Alkyd Resin A.

Propylene glycol- Alkyd Resin C tetrabromophthalate (parts by weight)Propylene glycol 68.2 Maleic anhydride 65.0 Tetrabromophthalic anhydride140.0

The compounds are mixed and heated slowly to 190 C. and held at thistemperature for 3 hours, then raised to 200 C. until the acid number isat least 40 or lower.

EXAMPLE V EXAMPLE VI The procedure of Example V is repeated 22 timesindividually with the remaining respective monomers of Example ll,(A.2), (A3), (A.7), (A.8), (MAJ), (MAJ), (MA.3), (MAJ), (MA.8), (MAJO),(A.a), (Ab), (A.d), (AI), (MA.a), (MA.b), (MA.d), and (MAX). andmonomers l 5), (l6), (l7) and (18) of Example Ill, and in all casescrosslinked, infusible, insoluble polymers with self-extinguishingproperties are obtained.

EXAMPLE VII The procedure of Example V is repeated using 50 parts of CHCHCOOCH CBr CBrCH OH and there is obtained a clear thermoplastic,rubbery polymer which is soluble in chloroform and which isself-extinguishing. Similar results are obtained when the monomers (ll),(l2), (l3), (l4), (19), (20), and (21) of Example III are usedindividually in this polymerization procedure.

EXAMPLE VIII a. A mixture of parts of methyl methacrylate and 10 partsof CH CHCOOC(CH CBr CBrC(CH OOCHC CH is copolymerized by the procedureof Example V and there is obtained a self-extinguishing, crosslinkedcopolymer. A mixture of parts of methyl methacrylate and 5 parts of [CHC(CH3)COOCHCBI]2 is copolymerized by the procedure of Example V andthere is obtained a crosslinked, self-extinguishing copolymer. c. Amixture of 75 parts of methyl methacrylate and 25 parts of [CH C(CH)COOCl-l CH OCI-l CBr] is copolymerized with the procedure of Example Vand there is obtained a crosslinked, self-extinguishing copolymer.

d. A mixture of 50 parts of methyl methacrylate and 50 parts of CHCHCOOCH CH CBr CBrCH CH OH is polymerized by the procedure of Example Vand a thermoplastic self-extinguishing copolymer is obtained.

EXAMPLE lX Each of the procedures of Examples Vlll(a), VllI(b) andVlll(c) is repeated six times using individually instead of methylmethacrylate, the same weights of methyl acrylate, styrene,acrylonitrile, beta-cyanoethyl methacrylate and vinyl chloroacetaterespectively, and in all cases, crosslinked, selfextinguishing polymersare obtained.

EXAMPLE X a. To each of 50 parts of alkyd resins A, B and C respectivelyare added 50 parts of Cl-l C(CI-l )COOC(CH CBr CBrC(CHa)2OOCC( CH 3) 2and 0.20 parts of tertiary butyl hydroperoxide and fiberglass mats areimpregnated according to procedures well known in the art to 45 percentresin contents. A three-ply laminate is prepared and placed between twolayers of polyethylene film and cured for 2 hours at C. and 4 hours atC. The cured laminate when tested for flame-resistant properties byA.S.T.M. Method D-635-44 is found to be non-burning andself-extinguishing.

b. The procedure of Example X(a) is repeated but 25 parts of CH C(Cl-l)COQC(CH ),CBr CBrC(CH OOCC(Cl-l CH is replaced in separate tests by 30parts of styrene, methyl methacrylate, vinyl acetate, triallyl cyanurateand triallyl isocyanurate respectively, and in all cases, non-burning,self-extinguishing laminates are obtained.

c. The procedures of Examples X( a) and X(b) are repeated using insteadof monomer (MAJ) monomers (A.1), (A.2), (A.8), (MAJO), (A.a), (A.f) and(MA.a), and in all cases, self-extinguishing laminates are obtained.

EXAMPLE Xl Under a nitrogen atmosphere, 50 parts of [CH, CHCOOCH CBr],

L 2 containing 0.5 parts of azoisobutyronitrile is added to 20 parts ofpoly(cis-butadiene) and the mixture stirred at 25 C. until it ishomogeneous; then the mixture is heated at 70 C. for 10 hours and at 120C. for 16 hours and there is obtained a crosslinked self-extinguishingpolymerizate which is tough and exhibits impact properties.

EXAMPLE XII The following mixtures are first prepared:

i CS and 0.05 part of sodium dodecylbenzenesulfonate and alethylmethacrylate (A) CH =OHOOOOH CBn Benzophenone Methyl methacrylateBenzophenone and then irradiated with ultraviolet light from a l00-wattmer- 20 cury lamp until the mixtures become solid and hard. In bothcases, self-extinguishing polymers are obtained.

EXAMPLE XIII The following mixtures are first prepared:

Parts l CII: -ClICO0ClIzCBr 20 CHg=C-COO CH;

CH2=CHCOOCHePO(OCgH5)z Alkyd Resin B 60 [CH2=CI'ICOOC I2CCl2 20cng=cnooocinomon 5 Samples of mixtures (A), (B), (C) and (D) are placedin glass vials which are swept out with nitrogen and sealed, and theneach is exposed to the beam of a 1 MEV Vander Graaff accelerator andinsoluble, infusible, non-burning, self-extinguishing polymers areobtained at dosages varying from 4 to 8 megarads. Similar results areobtained when other sources of ionizing radiation are used, such as fromnatural or synthetic radioactive material, for example, from Cobalt 60or from the Varian type travelling wave linear accelerators or the typesof accelerators described in U.S. Pat. No. 2,763,609 and British Pat.No. 762,953.

When ml.-wood ply is impregnated and saturated with mixtures (A), (B),(C) and (D), then covered with 0.1 ml. polyethylene sheet and irradiatedto 6 megarads as above, and the polyethylene barrier sheet removed, theresulting cured, impregnated wood is found to be dense, water-resistant,selfextinguishing and non-burning.

EXAMPLE XIV A skein of 20 parts of cotton thread is placed in 500 partsof an aqueous solution containing 2.5 parts of NaOl-I, 2.5 parts ofhydrogen peroxide and the mixture heated with agitation at 65 C. undernitrogen for 3 hours. The thread is then removed, washed with water, anddried; there is obtained 31.8 parts of grafted threads, which, whensuspended and the ends are ignited, are self-extinguishing when thesource of flame is removed.

The polymerization products of the acrylate esters of this invention canbe represented as having a plurality of repeating units selected fromthe formulas wherein R, R, X, y, n and P are as defined above.

When P represents 01-1, the resulting repeating units do not formcrosslinks per se.

When the formulas have P representing CH C(R')COO- crosslinked repeatingunits will be present in the polymer molecules having a formula selectedfrom There are in addition to uncrosslinked repeating units in which Pis CH C(R')COO-.

For example, with the monomer used in Example V the polymer has aplurality of repeating units therein selected from -CH2OH -OH CHdooorncm OOCHsCBr 000cm Br and 000cm Br OH2=CH OH: H 5

When both ns in the basic formulas represent zero, these formulas can beabbreviated as:

CH. E-

OO' (OR2)y OXL P-(CR2) y X:

R! C.H2

and 00(CR;) CX

When P represents CH, CHCOO- in these abbreviated formulas repeatingunits in polymers produced from the monomers are selected from theformulas For the dihaiogens:

CH2J3 OO(CR2)y-CX and COO-(CR2) X tended to limit the invention to theexact details shown above except insofar as they are defined in thefollowing claims:

The invention claimed is:

l. The acrylic ester having a formula selected from class consisting of1 C OH2O(R )COO \CHRCHRO/n RT CX=CX(CR /0CHRCHR\ P /y /n and FL CH2C(R)COO \CHRCHRO/n OIL/y C O CXzCXz( R27y\- CHRCHR/n wherein R representshydrogen, methyl or X, R represents hydrogen or a monovalent hydrocarboncontaining one to 10 carbon atoms, X is a halogen selected from theclass consisting of chlorine and bromine, y represents an integer havinga value of l or 2, n is an integer having a value of 0 to 3 and at leastone :1

equals 0, and P represents OH or Cl-l C(R' )COO- 2. The acrylic ester ofclaim 1 in which n is zero and P is CH C(R)COO-.

3. The acrylic ester of claim 2 in which each y is one. 4. The acrylicester of claim 2 in which each y is two.

5. The acrylic ester of claim 2 in which each X is Br. 6. The acrylicester of claim 2 in which each X is Cl. 7. The ester of claim 3 in which(CR- is -CH 8. The ester of claim 3 in which each (CR, is

9. The ester of claim 3 in which (CR is 10. The ester of claim 4 inwhich (CR, is -CH,CH,-. 1 l. The ester of claim 4 in which each (CR is12. A polymerization product of the ester of claim 1 having a pluralityof repeating units therein selected from the class consisting of whereinR, R, X, y, n and P are as defined in claim 1.

13. A polymerization product of claim 12 in which P represents OH.

14. A polymerization product of the ester of claim 1 having a pluralityof repeating units therein selected from the class consisting of 323UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Dated May 23, 1972Patent No. 3 66 992 Inventor(s) Gaetano F. D'Alelio It is certified thaterror appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

T- In the Abstract, the formulas should read:

and

HO+CHRCHRO)?1(CR2-9CX2-CX2 (cR -9 (ocnRcnR-a ou Signed and sealed this17th day of October 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Commissioner of PatentsAttesting Officer

2. The acrylic ester of claim 1 in which n is zero and P isCH2=C(R'')COO-.
 3. The acrylic ester of claim 2 in which each y is one.4. The acrylic ester of claim 2 in which each y is two.
 5. The acrylicester of claim 2 in which each X is Br.
 6. The acrylic ester of claim 2in which each X is Cl.
 7. The ester of claim 3 in which (CR2)y is -CH2-.8. The ester of claim 3 in which each (CR2)y is .
 9. The ester of claim3 in which (CR2)y is .
 10. The ester of claim 4 in which (CR2)y is-CH2CH2-.
 11. The ester of claim 4 in which each (CR2)y is .
 12. Apolymerization product of the ester of claim 1 having a plurality ofrepeating units therein selected from the class consisting of whereinR'', R, X, y, n and P are as defined in claim
 1. 13. A polymerizationproduct of claim 12 in which P represents OH.
 14. A polymerizationproduct of the ester of claim 1 having a plurality of repeating unitstherein selected from the class consisting of